CN1108088C - Coating for the structured production of conductors on the surface of electrically insulating substrates - Google Patents

Coating for the structured production of conductors on the surface of electrically insulating substrates Download PDF

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Publication number
CN1108088C
CN1108088C CN96191105A CN96191105A CN1108088C CN 1108088 C CN1108088 C CN 1108088C CN 96191105 A CN96191105 A CN 96191105A CN 96191105 A CN96191105 A CN 96191105A CN 1108088 C CN1108088 C CN 1108088C
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China
Prior art keywords
coating
glass
substrate
electrically insulating
oxide layer
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Expired - Fee Related
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CN96191105A
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Chinese (zh)
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CN1165609A (en
Inventor
约尔格·基克尔海恩
布鲁诺·维特
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LPKECAD/CAM SYSTEM CO Ltd
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LPKECAD/CAM SYSTEM CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/253—Coating containing SnO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/505—Tin oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/87—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H01L23/49872—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing semiconductor material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/027—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed by irradiation, e.g. by photons, alpha or beta particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/211—SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/241—Doped oxides with halides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/24—Doped oxides
    • C03C2217/244—Doped oxides with Sb
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Non-Insulated Conductors (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Glass Compositions (AREA)

Abstract

A coating for the structured production of conductors on the surface of electrically insulating substrates, in particular for producing sensor elements and printed circuit boards. The coating is formed from a doped tin oxide layer having the composition Sn1-(y+z)AyBzO2, in which A is Sb or F and B is In or Al. The relative proportions in the coating of the dopants antimony (or fluorine) and indium (or aluminum) are defined by the limits 0.02<y+z<0.11 and satisfy the condition 1.4<y/z<2.2. The coating can be structured by ablation using electromagnetic laser radiation in the wavelength range 157-1064 nm. The creates an economical means for high resolution and waste-free structuring of insulating channels in thin, electrically conductive layers having high chemical, mechanical and thermal resistance on glass or ceramic substrates.

Description

The coating that is used for structured production of conductors on the surface of electrically insulating substrates
The present invention relates to be used on the electrically insulating substrate surface make lead with a fixed structure, particularly be used for making the coating of sensor element and printed circuit board (PCB), this coating is made of the stannic oxide layer that mixes, and its composition is Sn 1-(y+z)A yB zO 2, wherein A=Sb or F, B=In or Al, and relate to a kind of coating method of coating and the method for this coating further being processed into structurized lead.EP 0 280 362 A2 disclose such coating.
In the chip and the wafer art of microsensor, hybrid integrated circuit, display device etc., make lead with a fixed structure and play leading role.In these fields, generally adopt so-called grand master pattern (mask) to form structure.Grand master pattern is made backing material by frit usually and is constituted.Even or the uneven thin layer of evaporation one deck on the backing material, normally evaporation chromium must form structure with the form of suitable requirement then.At many other fields of electronics, consider as traverse net or cloth gauze, make thin layer on glass substrate especially or compound thin layer form that structure paid close attention to very much.What known already here is, for thin metal layer lining one deck lacquer of thick about 0.1 μ m to 0.2 μ m that will form structure, then with electron beam or laser beam, perhaps also via optical system, makes the enamelled coating exposure and develops.Finish a chemical corrosion operation then, remove the metal covering of exposure.
At the printed circuit board (PCB) manufacture view, learnt by DE4010244A1 already that lining one deck conductive paint on printed circuit board (PCB) will conduct electricity enamelled coating with laser then and be processed into trace-diagram.Then formed trace-diagram is metallized.
EP 0280362A2 has also announced the application of tin oxide coating on thin-film heating element on full surface.Wherein also narrated the codope of tin oxide, thereby made this rete can on thin-film heating element, be used for higher temperature with antimony and indium.As everybody knows, especially under higher temperature, stannic oxide layer and atmosphere (O 2, H 2O) interact, this can cause the marked change of conductivity.For making this stannic oxide layer at high temperature also can to wait mole number, promptly mix antimony and indium equally as the transparent membrane heating element of electric performance stablity.Here particularly point out, its amount must not differ more than 10% mutually.And, antimony content that rete has and the indium content 4.5mol% that respectively does for oneself.Improve conductance by antimony in this case, come the stable crystal defective by indium.
Task of the present invention is to make the thin conduction coating that can be overlayed on glass and the ceramic substrate, can high-resolution directly constitute insulated trenches and noresidue in the coating.In addition, give preparation this coating and to its further method for processing.
According to an aspect of the present invention, provide a kind of coating that is used for making on the surface of electrically insulating substrates with certain version lead, coating is Sn by composition 1-(y+z)A yB zO 2Doped tin oxide layer constitute, wherein A=Sb or F, B=In or Al is characterized in that the dopant antimony of coating or the content that fluorine adds indium or aluminium are limited by 0.02≤y+z＜0.11, and the ratio of dopant 1.4＜y/z＜2.2 that satisfy condition.
According to a further aspect in the invention, provide a kind of method of making above-mentioned coating, it is that the thickness of coating is between 50nm and 500nm on 400 ℃ to 600 ℃ the substrate that the series of strata that wherein are covered are overlayed on surface temperature with the aerosol spraying method.
According to another aspect of the invention, provide a kind of and used above-mentioned coating manufacturing and have the method for the lead of a fixed structure, wherein carried out etching and make coating form structure with the electromagnetism laser emission in 157nm to the 308nm wave-length coverage.
The content that adds indium or aluminium by dopant antimony or fluorine in the coating is given by limiting value 0.02＜y+z＜0.11, and and 1.4＜y/z＜2.2 that satisfy condition of the ratio by dopant, what realize unexpectedly is: this rete is through with the laser emission etching in 157nm to the 308nm wave-length coverage, can not have residue and constitutes the structure with insulated trenches with high-resolution.
In addition, this task is finished by a method, it is characterized in that: at the bottom of the glass, pottery or the semiconductor silicon electrically insulating substrate that are deposited on 400 ℃ to 600 ℃ of surface temperatures under 400 ℃ to 600 ℃ a certain temperature, thickness is between 50nm and 500nm with aerosol spraying method (Aerosol-Spruehpyrolyse-Verfahren) for coating.
With the conductive structures that the electromagnetism laser emission etching in the described wave-length coverage forms, it is characterized in that the wall of the vertical and sharp edge of insulated trenches, and rete there is unusual good stable to chemical agent and mechanical and heat load.Coating of the present invention can be used for transducer, the humidity sensor of car front screen for example, and the lead that is used for microelectronic circuit, be specially adapted to the high-frequency component on the quartz glass substrate here, and for example be used as display device with the liquid crystal display layer combination.Form technology by special lining and structure, especially antimony (Sb) and the indium (In) by adding to the tin oxide normal concentration can be obtained high conductivity and high corrosion resistance simultaneously.Under the situation that keeps normal concentration, also available fluoro is used the aluminium substitution indium for antimony.
Confirmed already that rete had Sn 0.919Sb 0.052In 0.029O 2Composition suitable especially.Just as confirm that a kind of like this coating particularly has best electrical conductivity, available in addition excimer laser is made the sharp etching in high-resolution, noresidue and corner.This rete is deposited on glass substrate surface, and electric conductivity and metal are close, and transparent, and it also has unusual high corrosion resistance and mechanical strength.
Coating should be with the lining of aerosol spraying method under 400 ℃ to 600 ℃ temperature.Coating thickness is between 50nm and 500nm.The krypton fluoride excimer laser that a rete preferred implementing form wavelength according to the present invention subsequently is 248nm carries out etching and forms structure.
Further expansion of the present invention is that the regulation substrate is made of quartz glass, glass ceramics, Bohemian glass (particularly borosilicate Bohemian glass), suitable soft glass, pottery (particularly aluminium oxide ceramics) or semiconductor silicon.
It is that 3.6eV thereby visible light permeable semiconductor for example are used for transducer as the rete that can form fine structure that the present invention can make this band gap of tin oxide.Here used known effect, promptly in tin oxide, mixed suitable dopant and can produce for semiconductor unusual high flowed freely electron density (10 nearly 21/ cm 3).If this doped stannum oxide is deposited on the glass substrate with thin layer form, these electrical insulation glass just obtain almost as metal, conduct electricity, be again transparent coating simultaneously.
The present invention finds, the stannic oxide layer that preferably contains 5.2mol% antimony and 2.9mol% indium can be without a doubt, accurately form structure with excimer laser, and electrochemistry and stable mechanical performance later on.Proved already that the rete of gram-molecular weight antimony and indium such as for example mixing then can not had any problem forming on the structure with excimer laser.In addition, compare with the rete that meets the present art, the conductivity and the mechanical adhesion of the rete that the present invention now releases have advantageously improved.
Beyond thought completely is that the coating that the present invention adopts can be made the fine structure etching with excimer laser.Particularly metal owing to binding energy height or the like reason, can not adopt excimer laser to carry out the noresidue etching so far economically.If consider the interaction mechanism of laser beam and material, then optical maser wavelength is at first at material internal excitation oscillation mode, thereby for example METAL HEATING PROCESS arrived liquid state or gaseous polymerizable state.Carrying out heat at last removes quarter.This method particularly also can not be suitable for owing to inevitably the metal deposit is arranged for forming high-resolution structure.Therefore, use the scope of excimer laser to rest on all the time in the scope of degrading polymer so far economically.The situation that produces thermal effect with laser emission is different, is to offset the binding energy of molecule and particle and molecule cold cracking are separated for polymer.What this related to is non-pattern of fever etching process.
Owing to described reason, can not expect to obtain adopting the advantage of excimer laser fully in the blended metal oxide field in the past, especially can not look to the stannic oxide layer that adopts excimer laser to come etching the present invention to adopt fruitfully.Be to make humidity sensor, the patent applicant tests the similar rete of availability performance such as chromium nitride layer and directly forms structure and do not succeed eventually.This shows more, owing to the evaporation of material, deposits in the district that is etched when adopting excimer laser here.Therefore, fail to utilize the material of laser support to be etched into workable transducer so far.
Yet, just as unexpectedly show like that, a pulsed excimer laser is applicable to very that economically quilt that direct etching is developed into now overlays on glass or the ceramic substrate and the special coating of tool composition of the present invention.Form the extra high noresidue structure of resolution in the micron order zone of the thin stannic oxide layer that this can be covered on sheet glass or potsherd.This coating adopts excimer laser directly to form structure or finishes under application is arranged on the situation of the mask in the light path, and the region shape of the saturating laser emission of mask and structure are regional corresponding with the rete of answering etching; Perhaps finish with a laser beam that focuses on.
According to an example in detail the present invention is described in detail below.
The coating that the present invention adopts is overlayed on the substrate according to the aerosol spraying method.At this moment utilize commercially available sprayer unit to make the jetting fluid pneumatic nebulization become aerosol.Working gas adopts drying nitrogen.The average diameter that aerosol particle drips is in the number micrometer range.With the XY transmission device nozzle is being moved on the distance of 10cm to 15cm perpendicular to the glass substrate that lies in a horizontal plane on the flat stove.Slide is covered after cleaning in advance with a kind of known glass cleaner.This substrate is heated to surface temperature and is about 550 ℃ in a stove.This temperature is suitable especially, rises and obviously increase with temperature because the ratio conductivity of the rete that is covered is general.
Jetting fluid of the present invention is pressed following preparation: at 100cm 3At first dissolve 20cm in the n-butyl acetate 3Stannic chloride SnCl 4Dissolve 2.10g antimony chloride SbCl subsequently 3And 1.14g inidum chloride InCl is as dopant.
During lining, the chloride that contains in the solvent mainly utilizes pyrolysis to convert on fervid substrate surface to have composition Sn of the present invention 0.919Sb 0.052In 0.029O 2Sull.At this moment gained tin oxide thickness is 140nm to 400nm.
The one Pyrex plate thickness that has been covered is the doped tin oxide layer of 140nm.The sheet resistance of this layer is 93 Ω.Other of this layer are characterized as :-crystal structure: polycrystalline, tin face (rutile structure)-average visible light transmission rate:＞85%-refractive index: 1.95 ± 0.03-visual optical quality: transparent, no scattering does not have striped and some piece to fall into-micro-200 times of following flawlesses-adhere to: anticol band and rubber wiping-chemical stability: the acid of water insoluble, dilution or alkali (HNO particularly 3,
H 2SO 4, HCl; NaOH, KOH), at the aqueous solution of salt
(NaCl does not corrode in KCl), and is steady to commercially available glass cleaner
Fixed, difficult electrolytic corrosion in moisture NaCl/KOH is at root
According to stable in the salt mist test of DIN.-stable sheet resistance: in the air at least to 400 ℃ stable, do not find during with water-wet
The temperature coefficient of variation-sheet resistance: 3 * 10 4K -1(is benchmark with 20 ℃)-microhardness does not record Bohemian glass to increase and (records on soft glass obviously
High hardness)
Here the stannic oxide layer on Xu Shu the borosilicate substrate forms structure with excimer laser system, to make wetting transducer, is to make car wiping-washing transducer here.
The laser system that Adopting the structure of laser to form primarily being characterised in that of technology adopts an excimer laser and combines with mask projection. adopts has following technical parameter: laser type: KrF excimer laser wavelength: 248nm pulse width: 3 to 25ns maximum impulse energy: 460mJ mean power: 70W pulse peak power:＞18MW repetition rate: 200Hz divergence: 2 * 3mrad beam cross section: (7-10) * and 20mm2Energy stability: ± 4%
Another kind method is that an employing excimer laser and a focusing arrangement are combined.This equipment and technology has the advantage that forms structure very neatly.Mask projection technology and focusing processing all can realize with excimer laser in principle.These technology are known.The above also is applicable to the mirror deflection system that may adopt.
The present invention utilizes excimer laser to develop without a doubt to the material etching of stannic oxide layer.Particularly unexpectedly show no sign of and see that the film material deposition that is evaporated is arranged in insulated trenches, therefore can produce very fine structure and without any need for finishing.Etch away the backing material that the degree of depth reaches 20nm in insulated trenches with interior attaching.The feature that insulated trenches in the stannic oxide materials has is almost vertical wall and sharp-pointed visual limit (Sichtkanten).The sheet resistance of rete of the present invention is about 50 Ω to 150 Ω.
Car wiping-washing transducer of making is very sensitive, is enough to survey the mist pearl of coveing with the part.In addition, test shown good scuff resistance to dry friction, to the abundant stability of commercially available glass cleaner and car wash product and in salt mist test, the carrying capacity of environment test of auto industry regulation with electroplate enough durabilitys in the test.
Through replenish measuring, overlayed on the Pyrex, thickness is the stannic oxide layer of 140nm, its resistivity has only small growth.At present the crystallite dimension of this point owing to the polycrystalline film layer structure increased and some increase with bed thickness.Therefore, to thickness be the rete of 360nm to record sheet resistance be 30 Ω, rather than 36 Ω of expection.
In view of the composite glass of car front screen is to make this fact on the basis of soda lime glass (soft glass), the present invention also has the task of making the sensor on the soft glass substrate especially.The realization of the transducer on the soft glass substrate will be narrated as another embodiment of the present invention below.Only be that process for coating need be adjusted under this occasion, so only narrate the distinctive difference of substrate when being covered.
Comparing with Bohemian glass, wherein is that soft glass has much higher alkali metal oxide content, especially Na 2O content.As you know, since the temperature more than 450 ℃, sodium as small ion in a large number to the soft glass diffusion into the surface.If at this moment carry out tin oxide lining under 500 ℃ to 550 ℃ surface temperatures of the present invention, just form an intermediate layer that contains sodium, this intermediate layer is owing to sodium has high resistivity with the character that free electron in the tin oxide combines.Therefore, form the stannic oxide layer that contains sodium when hanging down lining speed, this can make sheet resistance when bed thickness is in the 100nm scope in M Ω scope.The transfer layer that the spectrophotometry alleged occurrence is such.
But, for example select the height of the about 52nm/min speed that is covered during for 7min in the lining time, just obtain the low-resistance rete of thick 360nm, sheet resistance (128 ± 6) Ω.This lining is to finish under 500 ℃ of lining temperature.Can make the car front screen plate transducer of working very effectively with this rete.For the stress of avoiding temperature deformation to cause makes the glass sheet breakage of applying in the film, it is advantageous carrying out the rete lining immediately at the cooling stage of glass factory's float glass.So just can avoid debatable soft glass heating.
The scope of application of the present invention in principle is confined to humidity sensor by no means, also may be used to make the lead of electronic circuit.Perhaps also might electroplate or the reducing process plated film stannic oxide layer of the present invention with conductor materials such as copper, gold, platinum.For the lead of electronic circuit, doing such thickening, to reduce conductor resistance can be favourable.N type electricity of the present invention leads stannic oxide layer and these metals constitute the minimum ohmic contact of resistance.In addition, use the very little quartz glass of dielectric loss also to suit here as the conductor structure that substrate is used for making high-frequency circuit.Stannic oxide layer of the present invention all substrates general and described here constitute very firm complex, because realized stable chemical bond on surface separately.
Another suitable expansion of the present invention is to make the structure that shows usefulness on soft glass and Bohemian glass.At this moment, form the transparent electrode structure of the tin oxide of structure as liquid crystal film (LCD).In addition, also may be applied in the display device of other electrostatic control.At last, also may be the stannic oxide layer of described formation structure as the heating element that forms structure.Except that the humidity transducer, other sensor application for example also has the micro-structural gas sensor.On these gas sensors,, must do different heating to each air chamber for realizing selectivity to some gas.

Claims (9)

1. be used for making on the surface of electrically insulating substrates with certain version the coating of lead, coating is Sn by composition 1-(y+z)A yB zO 2Doped tin oxide layer constitute, wherein A=Sb or F, B=In or Al is characterized in that the dopant antimony of coating or the content that fluorine adds indium or aluminium are limited by 0.02≤y+z＜0.11, and the ratio of dopant 1.4＜y/z＜2.2 that satisfy condition.
2. the described coating of claim 1 is characterized in that the coating composition is
Sn 0.919Sb 0.052In 0.029O 2。
3. claim 1 or 2 described coatings is characterized in that coating thickness is between 50nm and 500nm.
4. the described coating of claim 1 is characterized in that substrate is made of quartz glass, glass ceramics, Bohemian glass, soft glass, aluminium oxide ceramics or semiconductor silicon.
5. the described coating of claim 4 is characterized in that, described Bohemian glass is the borosilicate Bohemian glass.
6. the manufacture method of the coating of claim 1, it is that the thickness of coating is between 50nm and 500nm on 400 ℃ to 600 ℃ the substrate that the series of strata that it is characterized in that being covered are overlayed on surface temperature with the aerosol spraying method.
7. the described method of claim 6 is characterized in that the cooling stage that coating ties up to the substrate manufacturing is layed onto on the substrate.
8. application rights requires 1 to 4 each described coating manufacturing to have the method for the lead of a fixed structure, it is characterized in that carrying out etching with the electromagnetism laser emission in 157nm to the 308nm wave-length coverage makes coating form structure.
9. the described method of claim 8 is characterized in that with wavelength being that the KrF of 248nm carries out etching and makes coating form structure.
CN96191105A 1995-09-21 1996-09-18 Coating for the structured production of conductors on the surface of electrically insulating substrates Expired - Fee Related CN1108088C (en)

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KR100268122B1 (en) 2000-10-16
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DE19535068A1 (en) 1997-03-27
EP0793903A1 (en) 1997-09-10
JPH10501104A (en) 1998-01-27
ES2116817T3 (en) 1998-07-16
WO1997011589A1 (en) 1997-03-27

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